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Identifier

000462812

Title

Ανάπτυξη και μελέτη (μακρο)κυκλικών ενώσεων: πρόσβαση σε ατροποϊσομερή υψηλής ενέργειας περιστροφής

Alternative Title

Development and study of (macro)cyclic compounds: access to high rotational energy atropisomers

Author

Φραγκιαδάκης, Μιχαήλ Π

Thesis advisor

Νεοχωρίτης, Κωνσταντίνος

Reviewer

Στρατάκης, Μανώλης
Βασιλικογιαννάκης, Γεώργιος
Σμόνου, Ιουλία
Στούμπος, Κωνσταντίνος
Λυκάκης, Ιωάννης
Βουγιουκαλάκης, Γεώργιος

Abstract

The present PhD thesis is divided into five subsections (chapters), the main focus of which is the development of synthetic methodologies and the study of new heterocyclic and macrocyclic systems via multicomponent reaction chemistry (MCRs). Particular emphasis has been placed on the application of this chemistry towards the synthesis of high rotational energy atropisomers. More specifically: In Chapter 1, the potential of α-metalated isocyanides in the opening of lactones and cyclic anhydrides to form oxazole derivatives under basic conditions was examined. Three different isocyanides were used, in the presence of n-BuLi, aiming at the opening of lactone and cyclic anhydride rings towards the formation of the corresponding oxazoles. In Chapter 2, the synthesis of benzodioxepinones is reported through a one-pot procedure. Derivatives of salicyl acids were formed via a Williamson reaction between salicyl aldehydes and chloroacetic acid. These derivatives bear two functional groups, a formyl group and a carboxylic acid. Addition of an isocyanide in dichloromethane leads to the formation of benzodioxepinones through a Passerini reaction. In Chapter 3, the synthesis of macrocyclic compounds through multicomponent reactions is reported. Taking advantage of the dual nature of tosyloxy-protected isocyanides and the presence of nucleophilic centres in one of the reacting molecules, several multicomponent reactions were carried out. Initially, through a GBB-3CR reaction followed by cyclization transformations, compounds with 9-13 membered rings were formed., Compounds with 11-14 membered rings were formed through US-4CR and U-4CR reactions, while compounds with 7-10 membered rings were formed through UT-4CR reactions. In Chapter 4, the carbon dioxide trapping by imidazo heterocyclic derivatives resulting in the formation of cyclic carbamates was examined. Through a GBB-3CR reaction the corresponding derivatives were formed, which, in presence of carbon dioxide or carbonate salts, formed the corresponding 6-9 membered carbamate rings. In Chapter 5, a new class of high-energy rotational atropoisomers was synthesized and studied via UT-4CR reaction. More than 35 compounds were synthesized, which were studied crystallographically and kinetically through NMR experiments. Furthermore, DFT studies were performed, from which bond rotation times and energies were calculated, as well as the energy differences in the conformations of the atropisomers.

Language

Greek

Subject

Atropisomers

Benzodioxepinones

Carbamates

Carbon dioxide

Macrocycles

Multicomponent reactions (MCRs)

Oxazoles

Όξινα ισονιτρίλια

Αντιδράσεις πολλών συστατικών (MCRs)